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Carbon Metal Fluoride Nanocomposites High-Capacity Reversible Metal Fluoride

Conversion Materials as Rechargeable Positive Electrodes for Li Batteries

Article in Journal of The Electrochemical Society · October 2003

DOI: 10.1149/1.1602454

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A1318 Journal of The Electrochemical Society, 150 共10兲 A1318-A1327 共2003兲
0013-4651/2003/150共10兲/A1318/10/$7.00 © The Electrochemical Society, Inc.

Carbon Metal Fluoride Nanocomposites

High-Capacity Reversible Metal Fluoride Conversion Materials
as Rechargeable Positive Electrodes for Li Batteries
F. Badway, F. Cosandey, N. Pereira, and G. G. Amatucci*,z
Department of Ceramic and Materials Engineering, Rutgers-The State University of New Jersey, Piscataway,
New Jersey 08854, USA

The structure and electrochemistry of FeF3 :C-based carbon metal fluoride nanocomposites 共CMFNCs兲 was investigated in detail
from 4.5 to 1.5 V, revealing a reversible metal fluoride conversion process. These are the first reported examples of a high-capacity
reversible conversion process for positive electrodes. A reversible specific capacity of approximately 600 mAh/g of CMFNCs was
realized at 70°C. Approximately one-third of the capacity evolved in a reaction between 3.5 and 2.8 V related to the cathodic
reduction reaction of Fe3⫹ to Fe2⫹. The remainder of the specific capacity occurred in a two-phase conversion reaction at 2 V
resulting in the formation of a finer Fe:LiF nanocomposite. Upon oxidation, selective area electron diffraction characterization
revealed the reformation of a metal fluoride. Evidence presented suggested that the metal fluoride is related to FeF2 in structure.
A pseudocapacitive reaction is proposed as a possible mechanism for the subsequent Fe2⫹ → Fe3⫹ oxidation reaction. Preliminary
results of FeF2 , NiF2 , and CoF2 CMFNCs were used in the discussion of the electrochemical properties of the reconverted metal
fluoride.
© 2003 The Electrochemical Society. 关DOI: 10.1149/1.1602454兴 All rights reserved.

Manuscript submitted November 1, 2002; revised manuscript received April 15, 2003. Available electronically August 15, 2003.

The Li-ion battery is the premiere high-energy rechargeable en-
ergy storage technology of the present day. Unfortunately, its high
performance still falls short of energy density goals in applications
ranging from telecommunications to biomedical. Although a number
of factors within the battery cell contribute to this performance pa-
rameter, the most crucial ones relate to how much energy can be
stored in the positive and negative electrode materials of the device.
The positive electrode of Li-ion batteries is dominated by the
layered Li intercalation compound, LiCoO2 . 1 LiCoO2 has a practi-
cal reversible specific capacity of 150 mAh/g. Alternative electrode
materials such as compounds and solid solutions consisting of
LiNiO2 2 and LiMn2 O4 3,4 have been introduced in the past. Although
the capacity of these materials does not exceed that of LiCoO2 to a
great extent 共⬍250 mAh/g兲, they are lower in cost and the latter is
more environmentally acceptable. For the past decade there has been
an extensive effort to search for new positive electrode materials.
Current focus is on layered manganese compounds of the general
formula LiMnO2 5 and phosphate materials of the general formula
LiMePO4 6 and Li3 Me2 (PO4 ) 3 7 where Me is a transition metal. Al-
though operating at a lower voltage and close to the same capacity
as present day LiCoO2 , these materials are of interest due to their
low cost and safety. However, little new ground has been revealed in
the quest for positive electrode materials of higher energy density.
The fundamental route to attaining the highest specific capacity
of an electrode is to utilize all the possible oxidation states of a
compound during the redox cycle. This can be done by way of a
reversible conversion reaction which proceeds
nLi⫹ ⫹ ne⫺ ⫹ Men⫹X ↔ nLiX ⫹ Me
Previously, such reversible conversion reactions were only shown to
be active for low-potential materials suitable for use as negative
electrodes. This was first demonstrated by Tarascon’s group for the
oxide and sulfide chalcogenides8 and later by our group for the
transition metal nitrides.9 However, limited reversible conversion of
the Cu with ␣-CuVO3 has been noted by Kamiya et al.10
The quest to increase the specific capacity of the positive elec-
trode would require adoption of reversible conversion to positive
electrode materials, necessitating at least a 1 V increase in output
voltage with respect to the previously demonstrated chalcogenide,
* Electrochemical Society Active Member.
z
E-mail: gamatucc@rci.rutgers.edu
and nitride materials. The output voltage of primary conversion re-
actions are rooted in basic thermodynamics and are well understood.
In general, an increase in the Me-X bond ionicity results in an in-
crease in the output voltage associated with Reaction 1. Therefore
the output voltage of Reaction 1 would expect to increase through
the highly covalent metal nitrides and sulfides, to the metal oxides,
through the inductive effect polyanions 共metal phosphates, metal
borates兲, and finally to the highly ionic metal fluoride and metal
chloride halogens.
Metal fluorides have been largely ignored as reversible positive
electrodes for rechargeable lithium batteries. This is due to their
insulative nature brought about by their characteristic large bandgap.
Iron trifluoride (FeF3 ) was first reported as showing limited electro-
chemical activity by Arai et al.11 Arai reported a capacity of 80
mAh/g from FeF3 in a discharge voltage region from about 4.5 to 2
V involving the Fe3⫹ to Fe2⫹ redox transition. The poor electronic
conductivity combined with a questionable ionic conductivity re-
sulted in the disparity between the observed reversible specific ca-
pacity of 80 mAh/g and the theoretical (1e⫺ transfer兲 capacity of
237 mAh/g. Since then, the fluorides have been discarded as useful
reversible positive electrode materials.
Our group has recently introduced the use of carbon metal fluo-
ride nanocomposites 共CMFNCs兲 to enable the electrochemical ac-
tivity of metal fluorides.12 The concept was rooted in the fact that
nanosized crystals have a high total material volume on the surface.
This surface contains a number of defects which can contribute sub-
stantially to enhanced electronic and ionic activity 共for example, see
Maier13兲. In addition to increased activity of the metal fluoride
关1兴 brought about by the drastic reduction in crystallite size, we have
electrically connected the grains of each through the use of highly
conducting carbon. Our initial studies have shown a major improve-
ment in the electrochemical activity of FeF3 in the 4.5-2.5 V region
such that we could recover 99% of the FeF3 theoretical capacity
共235 vs. 237 mAh/g兲 in the 4.5-2.5 V region with a total CMFNC
specific capacity of approximately 200 mAh/g. The capacity and
voltage was consistent with the reduction
Li⫹ ⫹ e⫺ ⫹ Fe3⫹F3 → LiFe2⫹F3 关2兴
We also recently presented evidence that FeF3 CMFNCs offered
excellent reversible specific capacity through a second reaction oc-
curring at 2 V. The combined specific capacities resulted in an ex-
ceptional total capacity of approximately 600 mAh/g. We reported
that this metal fluoride reaction was due to a reversible fluoride-
 Journal of The Electrochemical Society, 150 共10兲 A1318-A1327 共2003兲
based conversion reaction and could be utilized for positive elec-
trode technology. Herein we present details of this reaction along
with preliminary data of CMFNCs based on the transition metal
difluorides: FeF2 , NiF2 , and CoF2 .
Experimental
High-energy milling.—CMFNCs were fabricated by the high en-
ergy milling of R3̄C FeF3 共Alfa兲, and either expanded graphite 共Su-
perior兲, carbon black 共MMM Super P兲, or activated carbon 共Norit
A-supra兲. Stoichiometric mixtures 共metal fluoride: C, 85:15 wt %兲
were placed inside a hardened steel milling cell along with hardened
steel media. All cell assembly was done in He atmosphere. The
milling was performed for the designated times in a high-energy
mill 共Spex 8000兲. As-formed CMFNC samples were removed from
the milling cell in a He-filled glove box. Unless otherwise noted,
85/15% FeF3 :C CMFNCs fabricated by high-energy milling for 1 h
with activated carbon were utilized for general characterization.
Physical characterization.—XRD.—The structure of the materi-
als was characterized by X-ray diffraction 共XRD兲, utilizing a Scin-
tag X2 diffractometer with Cu K␣ radiation. In situ XRD was car-
ried out in a custom in situ cell developed by our group and utilizing
a Be window, details of which will be published at a later date. The
electrochemical cell was cycled at a constant current of 7.58 mA/g.
Three-hour scans were utilized resulting in a ⌬x of 0.115 共x in
Lix FeF3 ) per scan. Ex situ XRD was accomplished by disassembling
the electrochemical cell in a He-filled glove box and rinsing the
electrode in dimethyl carbonate 共DMC兲. The dried electrode was
then placed on a glass slide and covered with Kapton film using a
seal layer of vacuum grease.
Transmission electron microscopy.—The material microstructure
was analyzed by transmission electron microscopy 共TEM兲 utilizing
a Topcon OO2B and a Phillips EM30 microscope. Dark field 共DF兲
imaging techniques were used to image the size and distribution of
the various phases. In addition, selected area electron diffraction
patterns 共SAED兲 from various areas were obtained to determine the
structure of the phases present. SAED patterns were analyzed using
Process Diffraction software.14 Ex situ high-resolution TEM 共HR-
TEM兲 was performed on samples in various states of electrochemi-
cal conversion to determine crystallinity and crystallite size. TEM
samples were prepared by dispersing the milled powder in tetrafluo-
rocarbon and releasing a few drops of the liquid on a carbon film
supported on a copper grid. Ex situ TEM was accomplished by
disassembly of coin cells containing powder. The powders were
rinsed in DMC, and grids were prepared as described previously
except that dispersion was accomplished with the use of DMC. All
preparation was accomplished in an anhydrous atmosphere. The
grids were sealed under helium and transferred to the TEM chamber.
The final transfer to the TEM chamber consisted of less than 30 s
exposure to ambient atmosphere.
Electrochemical characterization.—Following the removal of
CMFNC samples from the milling cell in the He-filled glove box,
the samples were sealed in a vial and transferred to a dry room
关⬍1% relative humidity 共RH兲兴 for processing. Processing was per-
formed in a dry room so as to impede any potential CMFNC reac-
tion with atmospheric moisture. Electrodes were prepared by adding
poly共vinylidene fluoride-co-hexafluoropropylene兲 共Kynar 2801, Elf
Atochem兲, carbon black 共Super P, MMM兲, and dibutyl phthalate
共Aldrich兲 to the CMFNC in acetone. The slurry was tape cast, dried
for 1 h at 22°C, and rinsed in 99.8% anhydrous ether 共Aldrich兲 to
extract the dibutyl phthalate plasticizer. The electrodes, 1 cm2 disks
typically containing 57 ⫾ 1% CMFNC and 12 ⫾ 1% carbon black
were tested electrochemically vs. Li metal 共Johnson Matthey兲. The
Swagelock 共in-house兲 or coin 共NRC兲 cells were assembled in a He-
filled dry box using Whatman GF/D glass fiber separators saturated
with 1 M LiPF6 in ethylene carbonate:dimethyl carbonate 共EC:DMC
1:1 in vol兲 electrolyte 共Merck兲. The cells were controlled by Mac-
A1319
Figure 1. XRD patterns of FeF3 :C CMFNCs fabricated by high-energy
milling with 15 wt % activated carbon for 30 min and 1 h compared with
manual mixing. 共*兲 Marks impurity peaks related to FeF3 -3H2 O.
Pile 共Biologic兲 or Maccor battery cycling systems. Cells were cycled
under a constant current of 7.58 mA/g at 22°C, unless noted other-
wise.
Results
FeF 3-C CMFNCs.—Physical characterization.—FeF3 -based
CMFNCs were fabricated by high-energy milling FeF3 and activated
carbon, carbon black, or expanded graphite for 10, 30, 60, 240, and
360 min in a 85-15 wt % ratio. The various carbons were chosen for
their contrasting properties. Activated carbon is a meso- and mi-
croporous carbon with a surface area of 1700 m2/g, carbon black is
networked carbon with excellent electrical connectivity, and ex-
panded graphite is an acid-treated, partially exfoliated graphite with
excellent electric conductivity. All samples were analyzed by XRD
to study phase development. XRD patterns of FeF3 -activated carbon
CMFNCs fabricated for 30 min and 1 h, compared with a macro-
composite fabricated by manually mixing 15% activated carbon
with 85% FeF3 , are shown in Fig. 1. Substantial and systematic
broadening of the Bragg peaks occurred with increasing milling
times, as is clearly evident in the comparison of the 共012兲 Bragg
peaks. The XRD data reveals that FeF3 remained as the only signifi-
cant phase developed after milling up to 1 h; however, a small
quantity of FeF3 -3H2 O is present in the raw FeF3 which dissipates
after milling. The small amount of hydrated FeF3 may be residual
from the dehydration process which can be utilized to form
commercial-grade FeF3 . The destruction of this small amount of
hydrated FeF3 phase by the high-energy milling is not surprising.
Localized heating encountered by the sample during the milling pro-
cess is most likely beyond that of the dehydration temperature.
Milling the activated carbon sample for 4 h 共Fig. 2a兲 results in
the reduction of the Fe3⫹F3 phase through defluorination, as evi-
denced by the major phase of Fe2 ( 3⫹2⫹) F5 and minor presence of
Fe2⫹F2 . Milling for 6 h 共Fig. 2b兲 results in further dehalogenation
and formation of the major phase of Fe2⫹F2 . Regarding the alterna-
tive carbons for the CMFNCs, carbon black resulted in a small
degree of FeF2 at 4 h 共Fig. 2a兲 and an increasing amount at 6 h 共Fig.
2b兲. This is in contrast to the expanded graphite sample in which the
FeF3 composition was maintained. The dehalogenation may be re-
lated to adsorbed moisture, which is most prevalent in the activated
carbon, followed by the carbon black and then finally the expanded
graphite. The contrast in efficiency of the dehalogenation reaction
among the carbons makes it unlikely that the formation of CFx is the
product or is responsible for the resultant electrochemical properties.
This point is revisited in greater detail in the Discussion section.
Crystallite size was determined through application of the
Scherrer formula on the 共012兲 Bragg peak for CMFCS fabricated by
milling FeF3 with the three carbons for 10, 30, 60, 240, and 360
A1320 Journal of The Electrochemical Society, 150 共10兲 A1318-A1327 共2003兲

Figure 2. XRD patterns of FeF3 :C CMFNCs formed from high-energy mill-

ing for 共a兲 4 and 共b兲 6 h using 共i兲 activated carbon, 共ii兲 carbon black, and 共iii兲
expanded graphite as the carbon. Milling times are indicated within each
figure. FeF2 phase is denoted by *, Fe2 F5 is denoted by ∧ .

min. The resulting data of the Scherrer calculation is plotted in Fig.

3. The 6 h activated-carbon-based CMFNC was not included due to
the small quantity of FeF3 present. All samples demonstrated similar
evolution of crystallite size with milling time. 10 min milling times
result in a large reduction of crystallite size from ⬎150 nm to ap-
proximately 40-45 nm. Further milling results in a minimum in crys-
tallite size of 25-30 nm between 60 and 240 min. Bragg peak broad-
ening, which is the basis of the Scherrer calculation, can also be
affected by nonhomogeneous internal strains which may not be
trivial in a high-energy-milled sample. The Williamson-Hall 共W-H兲
calculation is typically utilized to deconvolute the two contributing

Figure 4. DF TEM image at 共a兲 low and 共b兲 high magnification of 85/15 wt
% FeF3 /activated carbon CMFNC fabricated by high-energy milling for 1 h.
Bright areas associated with presence of FeF3 共see text兲.

Figure 3. Crystallite size as a function of milling time for FeF3 :C CMFNCs
based on 共䊏兲 activated carbon, 共⽧兲 carbon black, and 共䊊兲 expanded graph-
ite.
factors. Due to poor peak intensity we were not able to run the W-H
calculation; therefore, TEM analysis was utilized to corroborate the
results of the Scherrer analysis.
The formation of a nanocomposite is supported by the DF TEM
image of a CMFNC fabricated by milling with activated carbon for
1 h 共Fig. 4a and b兲. The majority of the FeF3 domains 共bright areas
associated with diffracted intensity of the 共012兲 reflection of R3C
FeF3 ) were ⬍30 nm interdispersed with carbon. Further discussion
of the nanocomposite structure was previously presented9 and will
be presented in a following publication. Unexpectedly, it was found
that further milling results in an increase in crystallite size, as is
clearly seen in the trend established in Fig. 3.
 Journal of The Electrochemical Society, 150 共10兲 A1318-A1327 共2003兲 A1321

Figure 5. Comparison of discharge/charge voltage profiles of FeF3 :C

CMFNCs 共1 h activated carbon兲 at 22 and 70°C at 7.58 mA/g. Data shows
first full discharge after short initial charge to 4.5 V.

The particle size increase could be attributed to a mechanically

assisted coarsening effect assisted by heat generated within the cell.
Another plausible explanation for this seemingly contradictory be-
havior 共increase in crystallite size with extended milling兲 can be
extracted from the examination of the XRD patterns. We have
shown CMFNCs composed of activated carbon have a greater trend
in crystallite size increase after 60 min of milling 共Fig. 3兲, followed
by the carbon black and the expanded graphite sample. The identical
trend 共activated carbon ⬎ carbon black ⬎ expanded graphite兲 is
also found in the carbon’s tendency to dehalogenate to the reduced
phases of Fe2 F5 and FeF2 共Fig. 2a and b兲. Through analysis of the
convoluted Bragg peak full width at half maximum 共fwhm兲, the
Scherrer formula presents a composite value for the primary particle
sizes and does not give an indication of distribution. From TEM
analysis, we have found that CMFNCs have a wide range of crys-
tallite size 共1-30 nm兲. One can envision the dehalogenation reaction
occurring most immediately for the smallest FeF3 crystallite sizes
共⬍5 nm兲, thereby leaving the remainder as larger FeF3 crystallites.
As a result of the lack of small crystallites, the Bragg peaks narrow
in the CMFNCs showing significant second-phase development 共de-
halogenation兲 and result in a false impression of growth in crystallite
size.
Electrochemical characterization 1.5-4.5 V.—The electrochemical
activity of the 85/15 wt % FeF3 :C CMFNCs was investigated in the
region between 4.5 and 1.5 V (Li/Li⫹) to explore the feasibility of a
reduction reaction from Fe3⫹ to Fe 共Fig. 5兲. Besides the initial Fe3⫹
to Fe2⫹ reaction in the voltage range between 4.5 and 2.5 V we
previously investigated,12 there exists a plateau development at ap-
proximately 2 V resulting in a total specific capacity of 367 mAh/g
共Fig. 5兲. This reaction was found to be reversible. The 2 V ‘‘plateau’’
seemed to exhibit Li insertion limitations as evidenced by the cur-
vature developing toward the end of reaction. Another cell was fab-
ricated and the electrochemical activity was investigated at 70°C to
increase kinetics of the reaction. At 70°C 共Fig. 5兲, the specific ca-
pacity of the CMFNC increased significantly to 660 mAh/g. Evi-
dence clearly showed that the process was at least partially revers- Figure 6. Voltage vs. time plots for Li/LiPF6 EC:DMC/FeF3 :C CMFNC 共1
ible with at least two distinct oxidation reactions occurring at h activated carbon兲 cells cycled at 70°C and 7.58 mA/g as a function of
approximately 3.0 V. In addition, the voltage vs. capacity plot also milling time.
showed that the 3.8-2.8 V (Fe3⫹ → Fe2⫹) reduction reaction that
was observed for the virgin FeF3 :C nanocomposite was reversible.
This, combined with the coulombic efficiency of the charge process shown in the representative voltage profiles of Fig. 6. The manually
with respect to the discharge, suggests complete reoxidation to milled sample exhibited very poor performance. A dramatic increase
Fe3⫹. in the electrochemical activity develops after only 10 min of milling
All the FeF3 -based CMFNC samples were initially discharged to to form the CMFNC and reaches an optimum for the 1 and 4 h
1.5 V and subsequently charged to 4.5 V at 70°C at 7.58 mA/g. The sample. After the third cycle, the discharge capacity was analyzed
effect of the milling time to form the CMFNC on the electrochemi- for all CMFNC samples. The data was separated into two regions,
cal behavior of the activated carbon-based CMFNC samples is the specific capacity recovered between 4.5 and 2.5 V, and the
A1322 Journal of The Electrochemical Society, 150 共10兲 A1318-A1327 共2003兲
Figure 7. Distribution of the third discharge specific capacity of FeF3 :C
CMFNCs as a function of carbon type and milling time. Cells were cycled at
7.58 mA/g at 70°C.
specific capacity recovered from 2.5 to 1.5 V. This would graphi-
cally isolate the Fe3⫹ to Fe2⫹ and the Fe2⫹ to Fe0 reduction reac-
tions, respectively. These specific capacities 共based on weight of
complete nanocomposite兲 are shown in Fig. 7. Total CMFNC ca-
pacities after the third cycle exceeded 540 mAh/g 共631 mAh/g
FeF3 ) in a number of samples. Approximately one third of the ca-
pacity was recovered in the upper voltage area between 2.5 and 4.5
V. This behavior is consistent with the 1e⫺ process at high potential
vs. the 2e⫺ process at low potential. Comparison of the development
of the specific capacity of the samples 共Fig. 7 and 6兲 with the crys-
tallite size 共Fig. 3兲 clearly shows a strong and direct relationship.
The development of the extraordinary specific capacity is tied di-
rectly to the formation of a nanocomposite, as we have previously
shown in detail for the 3 V reaction in FeF3 -based CMFNCs.9
Specific capacity as a function of cycle number for the CMFNCs
milled for 4 and 6 h is shown in Fig. 8 and 9, respectively. The
highest capacities recovered were for the 6 h carbon black-based
sample with a second discharge capacity of 660 mAh/g for the com-
plete composite 共15% carbon black兲. Corrected for the weight of
FeF3 one gets 759 mAh/g. This agrees well with the theoretical
capacity of FeF3 共712 mAh/g兲. The slight excess in capacity could
be attributed to irreversible parasitic cathodic reactions occurring on
the carbon surface. This effect dissipated within two full cycles.
Most samples cycled in the 540 mAh/g range resulting in a cor-
rected specific capacity of 621 mAh/(g FeF3 ). These capacities are
approximately 400% greater than present day LiCoO2 . Even though
Figure 8. Composite specific discharge and charge capacities for FeF3 :C
CMFNCs formed by milling for 4 h. Cells were cycled between 1.5 and 4.5
V at 7.58 mAh/g at 70°C.
Figure 9. Composite specific discharge and charge capacities for FeF3 :C
CMFNCs formed by milling for 6 h. Cells were cycled between 1.5 and 4.5
V at 7.58 mAh/g at 70°C.
average voltage is low 共approx. 2.3 V兲, energy densities based on the
smaller 540 mAh/g specific capacity number result in 1242 Wh/kg,
a factor of two greater than LiCoO2 ’s 600 Wh/kg. This is the high-
est specific capacity nonsulfur positive electrode reported to date. In
addition, cycling efficiencies 共see charge/discharge specific capaci-
ties in Fig. 8 and 9兲 were very high, even at 70°C with high surface
area, highly active nanocomposites. Although specific capacities
were exceptionally high and efficiency was good, a noticeable fade
in capacity with cycle number did exist. Preliminary evidence sug-
gests that this condition can be addressed with improved electrolytes
and attention to electrolyte/active material interface.
Discussion
Discharge reaction mechanism.—Electrochemistry and
mechanochemistry.—With capacities reaching 712 mAh/g, the the-
oretical reduction capacity of FeF3 , there is little doubt that full
reduction of Fe3⫹ to Fe0 is occurring. The Fe3⫹ to Fe2⫹ reaction
mechanism was found to consist of a two-phase transformation fol-
lowed by a topotactic insertion reaction as suggested by in situ and
ex situ XRD and electrochemical characterization 共Eq. 2兲. Therefore,
as we enter the reaction of discussion at 2 V, we begin with LiFeF3 .
Reducing the Fe2⫹ in LiFe2⫹Fe3 to Fe0 would necessitate the break-
ing of all Fe-F bonds and result in significant structural rearrange-
ment. We analyzed by ex situ XRD the reaction products of the fully
lithiated sample to elucidate the reaction mechanism.
A FeF3 :C 1 h activated carbon CMFNC was reduced to 1.5 V.
The powder was removed in a He-filled glove box and washed in
DMC to remove excess salts. The powder was then analyzed by
XRD in a sealed glass slide to minimize atmospheric exposure. The
results are shown in Fig. 10. Two compounds were identified, LiF
Figure 10. XRD patterns of ex situ analysis of reaction products postelec-
trochemical and mechanochemical reduction of FeF3 :C CMFNCs with Li⫹
or Li 共see text兲.
 Journal of The Electrochemical Society, 150 共10兲 A1318-A1327 共2003兲
Figure 11. In situ XRD of FeF3:C CMFNC 共1 h activated carbon兲. Note
systematic decrease in 共104兲, 共110兲, and 共113兲 Li1 FeF3 intensity and the
corresponding increase in 共110兲 peak of Fe. 共.....兲 Placed as an aid to the eye.
and Fe. This is consistent with a thermodynamic conversion reaction
of the type
2Li⫹ ⫹ 2e⫺ ⫹ LiFe2⫹F3 → 3LiF ⫹ Fe 关3兴
The thermodynamics of such a reaction is consistent with the volt-
age at which the reaction was found to occur, as discussed shortly.
To further support the mechanism, the electrochemical reaction
was replicated through the use of mechanochemistry. Li metal was
placed in a mechanomilling cell with an activated carbon:FeF3 CM-
FNC in a 3:1 molar ratio under a He atmosphere. The mechanical
mill was run for 30 min and the sample was removed in the glove
box and put on a sealed glass slide for XRD analysis. The mecha-
nochemical results are plotted vs. the electrochemical results 共Fig.
10兲. The results are virtually identical, the formation of Fe and LiF,
therefore supporting the theory of a thermodynamically driven con-
version mechanism. This conversion, although destructive in nature,
coincides with a relatively small 16% volume expansion and there-
fore should not preclude its use in an electrochemical cell.
In situ XRD.—The development of the conversion reaction was
characterized by in situ XRD in order to determine whether an in-
termediate reaction takes place during the conversion reaction. The
initial lithiation reaction 共Reaction 2兲 to LiFeF2 occurring between
3.5 and 2.8 V has been previously characterized in the in situ analy-
sis down to 2.5 V.9 Figure 11 shows the in situ analysis from 2.5 to
1.5 V at 22°C. From x ⫽ 0.92 to 2.42 in Lix FeF3 , all the peaks
associated with the Li1 FeF3 phase systematically decrease in inten-
sity 关especially for the 共113兲 peak兴. Simultaneously, the development
of the Fe 共110兲 peak is found to systematically increase. Although
intensities are poor, these results suggest the final 2e⫺ transfer pro-
cess from Fe2⫹ to Fe0 proceeds in a straightforward two-phase con-
version reaction as described in Eq. 3.
Oxidation reaction and reversibility.—We have come to a deter-
mination of the mechanisms involving the reduction reaction. The
question remains as to what is the reaction mechanism of the oxi-
dation reaction supporting the reversibility. As discussed before, the
oxidation reaction is associated with approximately 3e⫺ transfer and
subsequent discharge reactions maintain characteristics of the initial
A1323
Figure 12. Ex situ XRD of FeF3 :C CMFNCs 共activated C 4 h兲 at various
states of charge. 共*兲 Refers to developing peaks.
FeF3 -based CMFNC, namely, a 1e⫺ reaction between 3.5 and 2.8 V
and a 2e⫺ reaction at approximately 2 V. Based on this limited
information we can state that it is likely the Fe0 is reoxidizing to
Fe3⫹. However, we cannot make a statement regarding the reconsti-
tution of the FeF3 phase in a reversible fluoride conversion process.
Ex situ XRD characterization.—During the conversion reaction at 2
V the CMFNC converted into an even finer nanocomposite of Fe
and LiF on the scale of 10-20 Å based on XRD and HRTEM analy-
sis 共discussed later兲. During oxidation, in situ XRD showed little
useful information except for the systematic decrease in the intensity
of the broad Bragg peak associated with disappearance of Fe. To
gain more insight into the reaction, the 4 h milled FeF3 :C CMFNC
utilizing activated carbon electrodes were made into three cells in
which one was discharged to 1.5 V, one recharged to 3.3 V, and one
recharged to 4.5 V at 70°C. The three cells were then disassembled
in a He-filled glove box and analyzed by XRD. The results are
shown in Fig. 12. The fully lithiated sample consisted of Fe and LiF
as in the previous sample described previously. During oxidation,
the foremost feature is the reduction in the intensity of the Bragg
peak at approximately 2.0 and 2.3 Å, associated with the disappear-
ance of the Fe and LiF phase, respectively. Also apparent is the
development of weak peaks at approximately 1.7, 1.8, 2.7, and 3.3
Å. Few of these peaks can be associated with the original FeF3
phase or the Li1 FeF3 phase present before conversion. Although of
weak intensity, a striking agreement of the peaks was found with
FeF2 . This is shown by comparing the delithiated sample with a
FeF2 CMFNC formed by milling FeF2 with activated carbon for 1 h
in a 85:15 wt % stoichiometry 共Fig. 13兲. It should be noted that most
of the ‘‘FeF2 ’’-like phase formation occurs by the 3.3 V scan.
Ex situ SAED characterization.—The ex situ XRD data used in the
previous analysis was of poor intensity. In addition, the 4 h sample
initially contained nontrivial quantities of FeF2 , which may have
reconverted. To confirm the phase development upon oxidation for
Figure 13. Ex situ XRD of FeF3 :C CMFNCs 共activated C 4 h兲 at 共a兲 full
charge compared with 共b兲 raw FeF2 :C CMFNC 共activated C 1 h兲.
A1324 Journal of The Electrochemical Society, 150 共10兲 A1318-A1327 共2003兲
the FeF3 CMFNC with more certainty, SAED, which has a higher
sensitivity than X-rays, was utilized to characterize electrochemi-
cally formed samples. The 1 h milled FeF3 :C CMFNC utilizing
activated carbon was made into four cells. One was discharged to
2.2 V (Li1.23FeF3 ), one discharged to 1.5 V (Li2.58FeF3 ), one re-
charged to 3.1 V (Li2.18FeF3 ), and one recharged to 4.5 V
(Li0.596FeF3 ), all at 70°C. Upon analysis, the SAED images and
resulting d-spacings of the samples portray striking contrasts, espe-
cially between the ones taken of the 1.5 and 4.5 V samples 共Fig. 14兲.
The sample at 2.2 V 共not shown兲 was observed to be mostly nano-
crystalline with crystals a few nanometers in size, as evidenced by
broad and diffuse diffraction rings. This was because ⬎1e⫺ was
transferred and the conversion reaction to LiF and Fe was underway.
The fully lithiated 1.5 V sample showed diffuse rings associated to
the full conversion product Fe and LiF 共Fig. 14兲; the nanocrystalline
nature of the composite is confirmed in the HRTEM image of the
discharged composite shown in Fig. 15a. d-spacings derived from
SAED spectra taken from two fields of the 1.5 V sample are shown
in Table I. Field 1 had d-spacings which all agreed well with that of
LiF and possibly small quantities of Fe. The second field had
d-spacings which agreed well with that of the Fe majority. Both
results were consistent with that of the ex situ powder XRD results
and the conversion reaction of Eq. 3.
The partial recharge to 3.1 V 共not shown兲 and full recharge to 4.5
V showed new rings associated with new d-spacings with a parallel
development in crystallinity as represented by more spot develop-
ment on the SAED pattern 共Fig. 14兲. The HRTEM image of Fig.
15b, although of limited field of view, also supports this trend. List-
ing of the d-spacings of the SAED spectra from the sample re-
charged to 4.5 V is shown in Table II for two different fields of
analysis. The peaks from both fields differ significantly from the
Figure 14. SAED images taken from
two fields each of FeF3 :C CMFNCs that
were discharged to 1.5 V (Li2.58FeF3 )
and recharged to 4.5 V (Li0.596FeF3 ) all
at 70°C. Major diffraction circles are la-
beled with their respective d-spacings in
共Å兲. Data from Tables I and II were de-
rived from these spectra.
fully discharged sample 共Table I兲. Analysis shows they agree well
with FeF2 and the previously described ex situ XRD data.
Lattice parameters were calculated on the basis of the
P42/mnm FeF2 structure. The peak at approximately 2.0共3兲 Å was
associated to a composite of residual Fe from lack of full reconver-
sion, and LiF which would be left as a 1 mol constituent 共see Eq. 4兲,
and finally the 共210兲 Bragg reflection from FeF2
3LiF ⫹ Fe → FeF2 ⫹ LiF 关4兴
The 共220兲 data point was not included in the calculation due to
potential convolution with residual LiF and/or Fe diffraction rings
共as explained later兲. The lattice parameter data 共Table I兲 showed a
good fit to an FeF2 -like structure with a slightly smaller c/a ratio
with respect to the JCPDS standard.
The only FeF2 peak which did not develop to a great extent in
the reconverted samples is the 共110兲 associated with the ordering of
Fe in the 关110兴. This may be due to orientation of the domains
within the SAED spot area or interlayer mixing of the Fe cations
upon reconversion. The latter could play a role in the decrease of the
c/a ratio. The ex situ XRD analysis of Fig. 13 showed that although
attenuated, the peak was present. We are investigating in more detail
the root of the attenuated 共110兲 reflection and the crystal chemistry
of the reconverted phase.
We have shown that XRD and, even more so, the SAED evi-
dence supports the reformation of an iron fluoride phase from the
LiF and Fe cathodic sweep reaction products 共Eq. 3兲. However,
evidence supports that the reconverted phase is related in structure
to Fe2⫹F2 , not Fe3⫹F3 as we expected. This revelation is com-
pounded with the added discrepancy that subsequent cycles show
that close to 3e⫺ are reversibly consumed in the course of the
 Journal of The Electrochemical Society, 150 共10兲 A1318-A1327 共2003兲 A1325

Table II. d-spacings derived from SAED analysis of two fields of

a FeF3 C CMFNC recharged to 4.5 V. JCPDS standard for FeF2 is
shown for reference. Lattice parameters are indexed to FeF2
structure; „210… was not utilized in calculation due to potential
convolution with Fe and LiF diffraction rings.

4.5 V Field 1 4.5 Field 2 FeF2 - P42/mnm

3.320 共110兲
2.661 2.694 2.700 共101兲
2.339 2.377 2.344 共111兲
2.034 2.014 2.101 共210兲
LiF 2.013 共220兲
Fe 2.014 共110兲
1.792 1.773 共211兲
1.706 1.660 共220兲
1.530 1.541 1.488 共310兲
1.482 共112兲
1.433 1.433 1.417 共310兲
1.219 1.213 共321兲
1.165 1.160 1.173 共222兲
a ⫽ 4.79 ⫾ 0.02 Å a ⫽ 4.85 ⫾ 0.03 Å a ⫽ 4.7 Å
c ⫽ 3.20 ⫾ 0.05 Å c ⫽ 3.15 ⫾ 0.03 Å c ⫽ 3.31 Å

form a FeF2 -based CMFNC. The material’s electrochemistry was

then evaluated at 70°C. This material also developed a reversible
3.5-2.8 V feature with comparable specific capacity 共620 mAh/g
based on metal fluoride weight only, Fig. 16兲 as compared to the
FeF3 -based CMFNC. This feature only develops after the conver-
sion process is completed; as such, the second discharge profile is
shown in comparison with the FeF3 CMFNC

FeF2 ⫹ 2Li ⫹ 2e⫺ → 2LiF ⫹ Fe 关5兴

The electrochemical feature at 3 V validates the possibility that FeF2

could be responsible for such a feature, but first one must be certain
that it is iron fluoride, which is the root of such a reaction.
The presence of a metal fluoride and carbon under high-energy
Figure 15. Ex situ high-resolution TEM images of FeF3 :C CMFNCs that
conditions may lead one to speculate that CFx can be formed. Al-
were 共a兲 discharged to 1.5 V (Li2.58FeF3 ) and 共b兲 recharged to 4.5 V
though traditionally not a reversible reaction, the 3 V range of inter-
(Li0.596FeF3 ) all at 70°C.
est in the reactions is consistent with the cathodic reaction identified
for a range of CFx compounds synthesized at low temperature. How-
ever, the evidence clearly suggests that CFx compounds play no role
electrochemistry as opposed to 2e⫺ that we expect for an FeF2 in the electrochemical activity explored in this manuscript.
phase reconversion. In addition, the reversible profile clearly shows The first evidence is found in the investigation of the metal fluo-
the 3.5-2.8 V region associated with the Fe3⫹ → Fe2⫹ reduction ride dehalogenation reaction which can easily be associated with the
along with the conversion at approximately 2 V associated with the formation of carbon fluorides
Fe2⫹ → Fe0 reduction. The former reduction reaction would not
be expected to occur in Fe2⫹F2 . In the following paragraphs we MeFx ⫹ C → CFx ⫹ Me 关6兴
enter an introductory discussion to try to explain this phenomena
and to rule out other hypothetical situations which can give rise to
such behavior.
As a first step, we investigated whether nanocomposites utilizing
FeF2 would show such behavior. Therefore, 85 wt % FeF2
⫺ 15 wt % activated carbon were high-energy milled for 1 h to

Table I. d-spacings derived from SAED analysis of two fields of a

FeF3 :C CMFNC discharged to 1.5 V. JCPDS standards for LiF
and Fe shown for reference.

1.5 V Field 1 LiF-Fm3m 1.5 V Field 2 Fe-Im3m

2.301 2.325 共111兲
2.011 2.013 共200兲 2.014 2.027 共110兲
1.420 1.424 共220兲 1.429 1.433 共200兲
1.207 1.214 共311兲
1.156 1.163 共222兲 1.163 1.170 共211兲 Figure 16. Comparison of second cycle voltage curves for FeF3 :C and
1.003 1.005 共400兲 1.001 1.013 共220兲 FeF2 :C CMFNCs showing distinct similarities. All cells were cycled at 7.58
0.922 共331兲 0.898 0.906 共310兲 mA/g at 70°C in LiPF6 EC:DMC and were precharged to 4.5 V.
A1326 Journal of The Electrochemical Society, 150 共10兲 A1318-A1327 共2003兲
Figure 17. Voltage vs. time for 共a兲 NiF2 :C and 共b兲 CoF2 :C 85:15 wt %
CMFNCs cycled at 7.58 mA/g at 70°C. ‘‘Spikes’’ in voltage were due to
unintentional periods of open-circuit condition which portray the poor kinet-
ics of the electrochemical conversion reaction.
It was observed that significant dehalogenation occurs with extended
milling times. Therefore, if the dehalogenation reaction is associated
with the formation of electrochemically active CFx , we would ex-
pect specific capacity to increase drastically as the milling times are
increased. This is not the case as Fig. 7 clearly shows the specific
capacity of the partly dehalogenated 共Fig. 2兲 6 h milled activated
carbon sample decreases. Within the same argument, the graphite-
based samples which exhibit very little dehalogenation 共Fig. 2兲 re-
veal very high specific capacity 共Fig. 7兲.
The second argument is that NiF2 and CoF2 have more oxidizing
power and should promote CFx formation and the 3 V profile if the
two were related. To prove this point we fabricated NiF2 and CoF2
CMFNCs utilizing an activated carbon matrix. Their electrochemi-
cal activity is shown in Fig. 17, which is in sharp contrast to the
activity of FeF2 CMFNC 共Fig. 16兲, namely, in the absence of the
3.5-2.8 V reduction reaction.
The evidence and subsequent arguments presented suggest that
CFx is not the origin of the electrochemical features observed in the
FeF3 -based CMFNCs. To be more conclusive in our determination,
we have removed carbon entirely from the nanocomposite system
and replaced it with an electrically conductive oxide. V2 O5 was
high-energy milled in 15 and 25 wt % quantities with FeF3 . Physi-
cal and electrochemical characteristics will be discussed in detail in
a future publication; however, Fig. 18 clearly shows that the vana-
dium oxide-based nanocomposite enabled the electrochemical activ-
ity of FeF3 in the same fashion as carbon 共Fig. 16兲. Therefore, in no
way can CFx be associated with the electrochemical characteristics
of the fluoride nanocomposites.
Now that CFx has been removed as a candidate for the observed
electrochemical activity, we now attempt to explain the 3 V feature
which is found both in the FeF2 -like material formed postconversion
of FeF3 , and from FeF2 itself.
The key to the explanation of the additional specific capacity and
the 3 V feature is to go to the root of the question which lies in the
Figure 18. FeF3 -based nanocomposites utilizing 15 and 25 wt % V2 O5 as
conductive matrix. Cell cycled at 7.58 mA/g at 70°C. Specific capacity is
based on weight of entire nanocomposite.
redox of the Fe transition metal. Within an FeF2 structure we have
behavior which is consistent with an Fe2⫹ → Fe3⫹ transition. One
possible mechanism would be the formation of FeOx F2⫺2x by elec-
trochemical decomposition of solvents. However, the covalency
brought about by the oxygen should evolve a separate redox reaction
which is approximately 1 V less than the corresponding fluoride
conversion reaction 共as shown in following section兲, thereby ruling
out this hypothetical mechanism.
One cannot ignore the effect of surface area and the associated
surface reactions. The reconversion of the cathodically formed
3LiF ⫹ Fe to anodically formed FeF2 leads to a nanocomposite
consisting of nanograins on the order of 5 nm. It is impossible to
estimate the true metal fluoride/electrolyte area of the reconverted
material, although it is not unrealistic to speculate a large percentage
of the grains have active interfaces. This high-surface-area compos-
ite could enable the oxidation of Fe2⫹F2 to Fe3⫹F2 by a pseudoca-
pacitive reaction. This reaction would consist of the PF⫺ 6 anion of
the salt adsorbed to form a surface entity Fe3⫹Fe2 (PF⫺ 6 upon the
)
anodic sweep. The pseudocapacitive behavior as an active mecha-
nism for the FeF2 oxidation is too lengthy to discuss in depth here
and will be discussed in more detail in the next paper of this series.
In short, it is a viable explanation for 共i兲 the additional specific
capacity and 共ii兲 the 3.5-2.8 V voltage feature developing in the
FeF2 phase upon reconversion of the FeF3 :C CMFNC.
Thermodynamics and ionicity.—The conversion reaction of the
Li1 FeF3 → 3LiF ⫹ Fe (Fe2⫹ → Fe0 ) reaction is consistent with a
thermodynamically driven reaction. Assuming a Gibbs free energy
of Fe2⫹F2 to be approximately equivalent with that of LiFe2⫹F3 the
calculation of the free energy of Eq. 3 is 2.44 V. Experimentally, a
slightly lower potential 共approximately 2 V兲 was found for the re-
action to proceed. This may be nestled in the slow kinetics of the
reaction as suggested by its temperature dependence. In addition, the
lithiated iron trifluoride is different in lattice energy than the FeF2 on
which the thermodynamic values of the calculation were based. The
thermodynamics of Reaction 7 is interesting
Li⫹ ⫹ e⫺ ⫹ FeF3 → LiF ⫹ Fe 关7兴
If the conversion reaction could occur directly from Fe3⫹ to Fe0 , the
theoretical output voltage would be 2.74 V at a capacity of 712
mAh/g 共1950 Wh/kg兲, thereby eliminating the unattractive two-step
process we have witnessed. However, even if the Fe3⫹ to Fe2⫹
lithium insertion process could be overcome, we would still be faced
with a two-step thermodynamically driven conversion process
Li⫹ ⫹ e⫺ ⫹ FeF3 → LiF ⫹ FeF2 2.90 V 关8兴
2Li⫹ ⫹ e⫺ ⫹ FeF2 → 2LiF ⫹ Fe 2.44 V 关9兴
 Journal of The Electrochemical Society, 150 共10兲 A1318-A1327 共2003兲
Figure 19. Discharge curve of FeF3 :C CMFNC 共activated C 1 h兲 compared
with that of Fe2 O3 . Both cells were discharged at 7.58 mA/g at 70°C.
Recently, the reversible conversion process of transition metal chal-
cogenides has been investigated by Poizot et al.8 and by our group
for nitrides.9 Due to the covalency of the chalcogenides and nitrides
the conversion reaction occurs at 1 V potential. The ionicity of the
Fe-F bond, compared with the Fe-O bond, which is of more covalent
character, results in a higher reduction potential, approximately
equivalent to that of Fe2⫹ ions in solution. This is exemplified in
Fig. 19 which compares the second discharge of the electrochemical
conversion of Fe3⫹ 3⫹
2 O3 with that of Fe F3 . Overall, there is an
approximate 1 V difference between the two conversion reactions.
This is excellent agreement with the potential as calculated utilizing
the Gibbs free energy of reaction for the following discharge reac-
tion
6Li⫹ ⫹ 6e⫺ ⫹ Fe2 O3 → 3Li2 O ⫹ Fe 共 1.63 V兲 关10兴
⫹ ⫺
3Li ⫹ 3e ⫹ FeF3 → 3LiF ⫹ Fe 共 2.74 V兲 关11兴
Examination of Fig. 19 reveals intrinsic similarities between the
voltage curves associated with these reactions sans the 1 V differ-
ence. During the Fe3⫹ to Fe2⫹ reduction reaction in the second
cycle, both reactions proceed in a single phase-like reaction span-
ning a 1 V voltage range. The similarity extends to the Fe2⫹
→ Fe0 reaction. For both the chalcogenide and halide, this reaction
proceeds in a two-phase conversion reaction reducing the divalent
iron to metallic iron. The similarity of the reaction is summarized by
the following equations
2Li ⫹ 2e⫺ ⫹ Fe2 O3 → Li2 Fe2 O3 关12兴
4Li ⫹ 4e⫺ ⫹ Li2 Fe2 O3 → 2Li2 O ⫹ Fe 关13兴
View publication stats
A1327
Li⫹ ⫹ e⫺ ⫹ FeF3 → LiFeF3 关14兴
2Li ⫹ 2e⫺ ⫹ LiFeF3 → 3LiF ⫹ Fe 关15兴
In summary, it is surprising that the fluoride-based reaction is
reversible. The potentials utilized during the anodic reaction are
much higher than the analogous oxide reaction. They exceed the
values to oxidize the Fe into the solution of the electrolyte.
Conclusions
The reversible conversion reaction of metal fluorides was en-
abled through the use of nanocomposites 共CMFNCs兲. The ability to
reversibly reduce to the metal and reform a metal fluoride opens a
new avenue to high-specific-capacity positive electrodes based on
the reversible conversion reaction for lithium battery applications.
Clearly this can be extended to other classes of highly ionic,
transition-metal-based materials.
At this early stage, the high capacities 共⬎600 mAh/g兲 of the
fluorides are only accessible at elevated temperature and/or low rate.
These issues will no doubt be addressed by attention to kinetics and
materials engineering, leading to more practical methods of nano-
composite production. However, based on the experimental data, we
believe the combination of fluoride and nanocomposite technology
offers an exciting avenue into the search for lithium rechargeable
batteries with energy densities double of today’s technology.
Acknowledgments
G.G.A. sincerely thanks the U.S. Government for its support of
this research. F.C. thanks P. Stodilman of EPFL Switzerland for use
of the electron microscopy facility.
Telcordia Technologies assisted in meeting the publication costs of this
article.
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